Polymeric polychloro-polyfluoroalkyl phosphonitrilates



United States Victor Mark, Riverside, Ill., assignor to Universal OilProducts Company, Des Plaines, 111., a corporation of Delaware NoDrawing. Application December 31, 1952 Serial No. 329,091

10 Claims. (Cl. 260-573) This invention relates to a novel class ofamines having surface active properties which are formed by thecondensation of a polyoxyalkylene glycol or alkylene oxide with a cyclichydrocarbon amine. The invention also relates to the ammonium saltsderived from the aboveindicated amines by reaction of the amine with anacidacting compound under conditions whereby the amine is converted tothe corresponding ammonium cationic salt thereof.

This invention concerns an homologous series of compounds characterizedas amines and their corresponding ammonium salt derivatives containingone or'two hydrocarbon substituents attached to the amino nitrogen atomas a hydrophobic group and containing one or two polyoxyalkylene chainsattached to the same nitrogen atom I as the hydrophilic portion of thecompound. These compounds in general have surface active properties andin particular instances act as detergents in aqueous solution. Oneseries of the present compounds,herein characterized as cyclichydrocarbon substituted amines, which act as non-ionic or slightlycationic surface active agents in aqueous solution, have the folowingstructure:

R1]! Ru! n -ii-N Another series of the present compounds have cationicproperties in aqueous solutions thereof and may be considered asammonium salt derivatives of the above substantially non-ioniccompounds. These compounds have the following general structure:

In the above compounds, R, R and R" are each and independently selectedfrom hydrocarbon groups containing from 1 to about 20 carbon atoms pergroup, said groups R, R and R" containing a total of at least 5 carbonatoms, A is an aromatic or hydroaromatic radical of either mononuclearor poly-nuclear structure, n and p are independently chosen numeralsselected from 0, 1 and 2, Z is 1 or 2, q is equal to 2-Z, m is awhole'numher having a value of from 2 to 5, y is a whole number having avalue from 2 to about 30, R' is selected from the group consisting ofhydrogen, alkyl and aralkyl containing froml to 20 carbon atoms, and Xis an organic or inorganic monoor polyvalent anionic radical such asformate, acetate, propionate, and other fatty acid deatent O 2,876,263Patented Mar. 3, 1959 rived anions, oxalate, laurate, phenylsulfonate,benzoate, naphthenate, nitrite, borate, sulfate, sulfonate, halide,nitrate, sulfite, carbonate, etc.

In one of its embodiments the present invention concerns a compoundselected from the cyclic hydrocarbonmonoand di-polyoxyalkyleneN-substituted monoamines and the ammonium salt derivatives thereof, saidcompound containing a cyclic hydrocarbon radical and at least oneomega-hydroxyalkylpolyoxyalkylene radical attached to the amino nitrogenatom thereof, the polyoxyalkylene radical being further characterized inthat it contains an average of from 1 to about 30 oxyallgylene units perradical, each unit containing from 2 to 5 carbon atoms.

A more specific embodiment relates to a composition of matter comprisinga compound having the structure of an N,N-dipolyoxyethylene-w-hydroxyethyl-alkylaniline, the alkyl substitutentof the aryl nucleus containing from about 6 to about 15 carbon atoms andeach of said polyoxypolyethylene N-substituents containing an average offrom 1 to about 20 oxyethylene units.

The compounds of the present invention which possess surface activeproperties and particularly detergency in aqueous solutions thereof maybe formed by several alternative procedures, although the procedureinvolving the following sequence of steps is generally considered themost direct in producing the preferred products of the present inventioncontaining one or two long chain alkyl substituents on the cyclichydrocarbon nucleus: (1) alkylating a cyclic hydrocarbon selected fromthe monoand di-cyclic aromatic hydrocarbons containing at least tworeplaceable nuclear hydrogen atoms with an olefinic hydrocarbonalkylating agent containing from 5 to about 9 carbon atoms in the caseof utilizing a di-nuclear cyclic hydrocarbon feed stock, and from about6 to about 20 carbon atoms per molecule in the case of utilizing amono-cyclic aromatic hydrocarbon, said alkylation being effected in thepresence of an alkylation catalyst at condensation reaction conditions,(2) subjecting the resulting alkyl-substituted cyclic hydrocarboncontaining one and not more than two long-chain nuclear alkylsubstituents derived from the olefini-c hydrocarbon alkylating agent tonitration at reaction conditions sufficient to introduce a single nitroradical on the cyclic hydrocarbon nucleus, (3) reducing the nitroradical of the resulting nitro alkyl cyclic hydrocarbon to an aminogroup by subjecting said nitration reaction product to hydrogenationthereby forming the amine corresponding to the nitro substitutedalkylcyclic hydrocarbon, and (4) thereafter reacting theamino-substituted alkylcyclic hydrocarbon with an alkylene oxide or apolyoxyalkylene glycol of the desired chain-length to form theomega-hydroxy-polyoxyalkylene condensation product of the cyclichydrocarbon amine. If the monoor dicyclic alkyl naphthenes are desiredas the alkyl substituted cyclic hydrocarbon alkylene chain is desired onthe amino nitrogen atom, the starting material is a secondary aminewherein one of the hydrogen atoms of the intermediate amine is replacedby a non-condensable hydrocarbon radical selected from alkyl, aryl,aralkyl, or alkaryl, which do not undergo condensation with the alkyleneoxide or polyoxyalkylene glycol reactant. The single, remaining hydrogensubstituent on the amino group therefore undergoes condensation with thealkylene oxide or glycol to form a monopolyoXyalkylene-substitutedamine. The product of the above series of reactions is a slightlycationic compound (i. e. ionizes slightly in aqueous solution due to thetervalent nitrogen atom in its structure) and is an effective watersoluble detergent. When a cationic product is desired, the previouslyformed intermediate product containing a tervalent amino nitrogen atomhaving an unshared pair of electrons is further reacted with anacid-acting compound which converts the unshared pair of electrons onthe amino nitrogen atom into a pair of electrons shared by a hydrogenatom or a hydrocarbon radical, thereby converting the cyclic hydrocarbonamine to an ammonium salt capable of ionizing in an aqueous solution toan ammonium cation associated with an anion derived from the acid-actingcompound. Thus, the slightly cationic amine compound may be reacted witha molar equivalent of an acid, such as hydrochloric acid, hydrobromicacid, nitric acid, benzene sulfonic acid and sulfuric acid, or withanother acid-acting compound such as an alkyl halide or aralkyl halideor sulfate to convert theamine into a cationic ammonium salt.

It is to be noted that although long chain alkyl-substitutedcyclic'hydrocarbon amines containing a single long chain alkylsubstituent having from about 5 to about carbon atoms per alkyl group onthe cyclic hydrocarbon ring, are generally the preferred species of thepresent surface active agents because of their highly effectivedetersive properties, the present invention also relates to otherspecies of compounds useful as wetting agents, emulsifying agents etc.which contain no long chain alkyl radical substituted directly on thecyclic hydrocarbon nucleus, but rather, in a hydrocarbon radicalsubstituted on the amino nitrogen atom. Other species of the presentseries of compounds are the polyalkyl substituted cyclic hydrocarbonamines, containing multiple nuclear alkyl substituents and one or twopolyoxypolyalkylene groups on the amino nitrogen atom. Thus, theinvention also concerns compounds of the type having the followinggeneral structure:

wherein n and p are zero, 'q is 1, and R" is alkyl containing'from l toabout 20 carbon atoms, aryl, aralkyl, or alkylaryl, said compounds'being effective wetting agents. When R" is a long chain alkyl group,such as a C to C radical, the products usually possess detergency. Stillanother species of this invention are the compounds represented by theabove formula in which n and p are at least '1 and qis zero or 1,provided that the sum of the number of carbon atoms in R and R and R" isat least 5 in order for the products to possess any significant degreeof detergency.

Other forms of the present products have the following structuralformula:

wherein the radicals R and R are alkyl groups containing from 1 to 20carbon atoms per" group and R has the same designation as above.Generally, it is preferred that when one of the groups: R, R or R" is along chain alkyl group containing 5 or more carbon atoms, the otherradicals of the group are hydrogen or short chain alkyl groups such asmethyl, ethyl, propyl, butyl, or amyl, although the eifectiveness of theproduct is not necessarily limited to such structural configurations.

Cyclic hydrocarbon compounds, comprising one of the primary chargingstocks to the alkylation stage of the present process in which theintermediate long-chain alkyl cyclic hydrocarbon is formed, arecharacterized generally as cyclic hydrocarbons containing at least 2nuclearly replaceable hydrogen atoms on the cyclic hydrocarbon nucleusand may in addition, contain other nuclear alkyl substituents. Typicalspecific examples of such cyclic hydrocarbons utilizable as the alkylacceptor reactant in the alkylation stage of the process include membersnot only of the benzene series, that is, the mono-cyclic aromaticcompounds, but also includes polycyclic aromatics such as, for example,members of the naphthalene series, the anthracene and phenanthreneseries, the biphenyl se ries, the tetrahydronaphthalene series, and thelike. Thus, typical compounds utilizable in the process include suchhydrocarbons as benzene, toluene, ethylbenzene, propylbenzene, (such ascumene and l-phenylpropane), butylbenzenes, such as l-phenyloutane,sec-butylbenzene, tertbutylbenzene; dialkylbenzenes such as ethyltoluencetc.; naphthalene; the various alkyl n'aphthalenes such as methyl andethyl naphthalene; phenanthrene and the'alkylphenanthrenes; thepartially hydrogenated polynuclear aromatic hydrocarbons containing atleast one aromatic ring, such as 1,2,3,4-tetra--hydronaphthalerie, etc.;and the higher alkyl-substituted cyclic hydrocarbons of the aboveseries. Compounds of this invention containing a naphthene ring or apartially hydrogenated polynuclear aromatic ring system are formed byhydrogenating the corresponding'aromatic compounds following theintroduction of the amino group into the ring of the aromatic compoundvia nitration and reduction of the nitro group to an amino radical.

The unsubstituted and lower alkyl-substituted cyclic hydrocarbonsutilizable as starting materials in the present process may generally beobtained from naturally occurring sources of hydrocarbons, for example,by separating the hydrocarbon from a petroleum-derived fraction, as inthe case of benzene, toluene, xylene, naphthalene, which are present inpetroleum crudes and particularly in certain fractions of reformed orhydroformcd gasolines. The higher alkyl cyclic hydrocarbons, containingone or more alkyl substituents of four or more carbon atoms per alkylgroup generally are difficult to separatein a pure form from naturallyoccurring sources of such hydrocarbons and generally must be produced bysynthesis from the unsubstituted or lower allryl substituted cyclichydrocarbons. One of the most readily available methods for synthesizinghigher (or long-chain) alkyl-substituted cyclic hydrocarbons involvesalkylating the unsubstituted or lower alkyl-substituted cyclichydrocarbon containing at least two nuclearly replaceable hydrogen atomswith an alkylating agent (preferably a mono-olefin) having an alkylgroup condensable with the cyclic hydrocarbon under alkylating reactionconditions. Thus, a long-chain alkyl group, for example one containingfrom 5 to about 20 carbon atoms per group, and gen erally not more thantwo of such groups, may be substituted on the cyclic hydrocarbon nucleusto provide an alkylate containing one or two long chain alkyl groups permolecule. Suitable olefinic hydrocarbon alkylating agents may beselected from the straight chain or branched chain olefinic hydrocarbonswhich may be ob tained from various sources, such as from petroleum and

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